Ortho‐C–H addition of 2‐substituted pyridines with alkenes and imines enabled by mono(phosphinoamido)‐rare earth complexes. (30th June 2021)

• Record Type: Journal Article
• Authors: Lin, Hailong; Li, Yongrui; Wang, Jinyu; Zhang, Mei; Jiang, Tao; Li, Jing; Chen, Yanhui
• Is Part Of: Applied organometallic chemistry. Volume 35:Number 10(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-06-30
• Subjects: alkenes -- C–H activation -- imines -- pyridine -- rare earth; Organometallic chemistry -- Periodicals; Organometallic compounds -- Periodicals; 547.05
• DOI: 10.1002/aoc.6345
• Languages: English
• ISSNs: 0268-2605

Abstract

Abstract: We here reported a special catalytic performance of mono(phosphinoamido)‐ligated rare earth complexes in ortho ‐C–H functionalization of pyridines with nonpolar alkenes and polar imines. Upon treatment with one equiv. of borate reagent B(C6 F5 )3 or [Ph3 C][B(C6 F5 )4 ], complex NP1‐Sc can act as an efficient catalyst for ortho ‐C–H alkylation of pyridines towards alkenes. In the presence of 1:1 mixed secondary amine of HN (SiMe3 )2 and HNBn2, complex NP2‐Gd can catalyze ortho ‐C–H addition of pyridines towards imines, effectively. A wide range of substrates were subjected to the catalysis to render the one step synthesis of a variety of ortho ‐alkylated and ortho ‐aminoalkylated pyridine derivatives in good yields and an excellent regioselectivity and chemoselectivity. Abstract : Mono(phosphinoamido)‐ligated rare earth dialkyl complexes, such as scandium or gadolinium complexes, were found to be as efficient catalyst precursors for ortho ‐C–H addition of 2‐substituted pyridines towards nonpolar alkenes or polar imines under mild reaction conditions, respectively.